CN113366668A - Doping system and doping method - Google Patents

Doping system and doping method Download PDF

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Publication number
CN113366668A
CN113366668A CN201980089878.8A CN201980089878A CN113366668A CN 113366668 A CN113366668 A CN 113366668A CN 201980089878 A CN201980089878 A CN 201980089878A CN 113366668 A CN113366668 A CN 113366668A
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doping
electrode
tank
recovery
roller
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直井雅也
小岛健治
相田一成
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Musashi Energy Solutions Co Ltd
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Musashi Energy Solutions Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
    • H01G13/04—Drying; Impregnating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Abstract

A doping system that dopes an alkali metal to an active material in an electrode in a band shape, wherein the electrode has a layer containing the active material. The doping system is provided with: the device comprises a doping groove, a conveying unit, a counter electrode unit, a connecting unit and a recovery unit. The doping tank contains a solution containing alkali metal ions. The transfer unit transfers the electrode along a path passing through the inside of the doping tank. The counter electrode unit is accommodated in the doping groove. The connection unit electrically connects the transfer roller of the transfer unit and the counter electrode unit. A recovery unit recovers the solution attached to the electrode having passed through the doping tank to the doping tank.

Description

Doping system and doping method
Cross Reference to Related Applications
This international application claims priority from japanese patent application No. 2019-9585, filed by the japanese patent office on 23/1/2019, the entire contents of which are incorporated herein by reference.
Technical Field
The present disclosure relates to doping systems and doping methods.
Background
In recent years, miniaturization and weight reduction of electronic devices have been receiving attention. Along with the miniaturization and weight reduction of electronic devices, there is a further increasing demand for miniaturization and weight reduction of batteries used as driving power sources for the electronic devices.
In order to meet the above-described demand for reduction in size and weight, nonaqueous electrolyte secondary batteries typified by lithium ion secondary batteries have been developed. Further, a lithium ion capacitor is known as an electric storage device for applications requiring high energy density characteristics and high output characteristics. Further, sodium ion batteries or capacitors using sodium which is less expensive than lithium and abundant in resources are also known.
In the above-described battery or capacitor, a process of doping an electrode with an alkali metal in advance (generally referred to as predoping) is employed for various purposes. As a method for pre-doping an electrode with an alkali metal, for example, a continuous method is available. The continuous method performs pre-doping while moving a strip-shaped electrode in a doping solution. Patent documents 1 to 4 disclose continuous methods.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 10-308212
Patent document 2: japanese patent laid-open No. 2008-77963
Patent document 3: japanese patent laid-open No. 2012 and 49543
Patent document 4: japanese patent laid-open No. 2012 and 49544
Disclosure of Invention
Problems to be solved by the invention
When the preliminary doping is performed, a strip-shaped electrode is transported along a path passing through a doping tank containing a doping solution. The electrode having passed through the doping tank is attached with a doping solution. That is, the electrode carries the doping solution out of the doping tank. If the amount of the doping solution carried out of the doping tank by the electrode is large, the amount of the doping solution used increases.
An aspect of the present disclosure is to preferably provide a doping system and a doping method capable of suppressing the amount of a doping solution carried out of an electrode from a doping tank.
Technical scheme for solving problems
One aspect of the present disclosure relates to a doping method that dopes an alkali metal to an active material in an electrode in a band shape using a doping system, wherein the electrode has a layer containing the active material. The doping system is provided with: a doping tank configured to accommodate a solution containing alkali metal ions; a transport unit configured to transport the electrode along a path passing through the inside of the doping tank; a counter electrode unit configured to be accommodated in the doping tank; a connection unit configured to electrically connect the counter electrode unit and a conveyance roller provided in the conveyance unit; and a recovery unit configured to recover the solution attached to the electrode that has passed through the doping tank, to the doping tank.
The doping method of one aspect of the present disclosure uses a doping system provided with a recovery unit. Therefore, the doping method of one aspect of the present disclosure can suppress the amount of the doping solution carried out of the electrode from the doping tank.
Another aspect of the present disclosure relates to a doping system that dopes an alkali metal to an active material in an electrode in a band shape, wherein the electrode has a layer containing the active material. The doping system is provided with: a doping tank configured to accommodate a solution containing alkali metal ions; a transport unit configured to transport the electrode along a path passing through the inside of the doping tank; a counter electrode unit configured to be accommodated in the doping tank; a connection unit configured to electrically connect the counter electrode unit and a conveyance roller provided in the conveyance unit; and a recovery unit configured to recover the solution attached to the electrode that has passed through the doping tank, to the doping tank.
The doping system according to another aspect of the present disclosure includes a recovery unit, so that the amount of the doping solution carried out of the doping tank by the electrode can be suppressed.
Drawings
Fig. 1 is a plan view showing the structure of an electrode.
Fig. 2 is a sectional view showing a section II-II in fig. 1.
Fig. 3 is an explanatory diagram showing the structure of the doping system.
Fig. 4 is an explanatory diagram showing the structure of the doping groove.
Fig. 5 is an explanatory diagram showing the structure of the counter electrode unit.
Fig. 6 is an explanatory diagram showing the structure of the recovery unit in the 1 st state.
Fig. 7 is an explanatory diagram showing the structure of the recovery unit in the 2 nd state.
Fig. 8 is an explanatory diagram showing the structure of the recovery unit of embodiment 2.
Fig. 9 is an explanatory diagram showing the structure of the recovery unit of embodiment 3.
Fig. 10 is an explanatory diagram showing the structure of the recovery unit of embodiment 4.
Fig. 11 is an explanatory diagram showing the structure of the recovery unit of embodiment 5.
Description of reference numerals
1 … electrode; 3 … current collector; 5 … active substance layer; 11 … doping system;
15 … electrolyte treatment tank; 17. 19, 21 … doping grooves; 23 … cleaning tank;
25. 27, 29, 31, 33, 35, 37, 40, 41, 43, 45, 46, 47, 49, 51, 52, 53, 55, 57, 58, 59, 61, 63, 64, 65, 67, 69, 70, 71, 73, 75, 77, 79, 81, 83, 85, 87, 89, 91, 93 … transport rollers; 101 … supply roller;
103 … winding the drum; 105 … supporting table; 107 … circulating filter unit;
109. 110, 111, 112, 113, 114 … power supplies; 117 … end purge;
119. 203, 205, 245 … recovery units; 121 … end sensor; 131 … upstream slot;
133 … downstream groove; 137. 139, 141, 143 … pairs of electrode elements; 149. a 151 … space;
153 … conductive substrate; 155 an alkali metal-containing plate; 157 … porous insulating member;
a 161 … filter; 163 … pump; 165 … piping; 171 … fixing part; 173 … rotating part;
175. 211, 221, 223, 251, 265, 267, 269, 271 … support plate;
177. 191, 213, 215, 225, 227, 253, 255, 257, 259, 273, 275, 277, 279 … removing the drum; 179 … transfer cylinder; 181 … drain roller; 183 … scraper;
183a … front end; 185 … liquid droplet guide plate;
187. 217, 235, 239, 261, 291, 295, 297, 299 … rotation axis;
189, 189 … supporting plate; 189a … body portion; 189B … stem; 193 … transfer cylinder;
195 … drain roller; 197 … scraper; 197a … front end; 199 … liquid drop guide plate;
207 … part 1; 209 part 2 of 209 …;
229. 231, 281, 283, 285, 287 … springs; 221a … body portion; 221B … stem;
241. 243 … liquid drop guide plate; 247 … part 1; 249 … part 2;
265a … body portion; 265B … stem; 267a … center; 267B … arm 1;
267C … arm No. 2
Detailed Description
Exemplary embodiments of the present disclosure are explained with reference to the drawings.
< embodiment 1 >
1. Structure of electrode 1
The structure of the electrode 1 will be described with reference to fig. 1 and 2. The electrode 1 has a strip-like shape. The electrode 1 includes a current collector 3 and an active material layer 5. The current collector 3 has a belt-like shape. Active material layers 5 are formed on both surfaces of the current collector 3.
As the collector 3, for example, a metal foil of copper, nickel, stainless steel, or the like is preferable. The current collector 3 may be a current collector in which a conductive layer containing a carbon material as a main component is formed on the metal foil. The thickness of the current collector 3 may be, for example, 5 to 50 μm.
For example, the active material layer 5 can be prepared by applying a slurry containing an active material, a binder, and the like to the current collector 3 and drying the slurry.
Examples of the binder include rubber-based binders such as styrene-butadiene rubber (SBR) and NBR; fluorine-based resins such as polytetrafluoroethylene and polyvinylidene fluoride; polypropylene; polyethylene; fluorine-modified (meth) acrylic adhesives and the like as disclosed in Japanese patent laid-open publication No. 2009-246137.
The slurry may contain other components in addition to the active material and the binder. Examples of the other components include conductive agents such as carbon black, graphite, vapor grown carbon fiber, and metal powder; such as carboxymethyl cellulose, Na or ammonium salts of carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and the like.
The thickness of the active material layer 5 is not particularly limited, and the thickness of the active material layer 5 may be, for example, 5 to 500 μm, preferably 10 to 200 μm, and particularly preferably 10 to 100 μm. The active material contained in the active material layer 5 is not particularly limited as long as it is an electrode active material that can be applied to a battery or a capacitor that utilizes insertion/extraction of alkali metal ions. The active material may be a negative electrode active material or a positive electrode active material.
The negative electrode active material is not particularly limited, and examples thereof include carbon materials such as graphite, easily graphitizable carbon, hardly graphitizable carbon, and composite carbon materials formed by covering graphite particles with a pitch or a resin carbide; and materials containing a metal or semimetal such as Si or Sn, or an oxide of the metal or semimetal, which can be alloyed with lithium. Specific examples of the carbon material include those described in Japanese patent laid-open publication No. 2013-258392. Specific examples of the material containing a metal or a semimetal capable of alloying with lithium or an oxide of the metal or semimetal include those described in japanese patent laid-open nos. 2005-123175 and 2006-107795.
Examples of the positive electrode active material include transition metal oxides such as cobalt oxide, nickel oxide, manganese oxide, and vanadium oxide; sulfur-based active materials such as elemental sulfur and metal sulfides. The positive electrode active material and the negative electrode active material may be composed of a single material or may be composed of a mixture of two or more materials.
The active material contained in the active material layer 5 is preliminarily doped with an alkali metal using a doping system 11 described later. As the alkali metal to be pre-doped into the active material, lithium or sodium is preferable, and lithium is particularly preferable. When the electrode 1 is used for manufacturing an electrode of a lithium ion secondary battery, the density of the active material layer 5 is preferably 1.50 to 2.00g/cc, and particularly preferably 1.60 to 1.90 g/cc.
2. Structure of doping system 11
The structure of the doping system 11 is explained with reference to fig. 3 to 5. As shown in fig. 3, the doping system 11 includes: an electrolyte treatment tank 15; doping trenches 17, 19, 21; a cleaning tank 23; conveying rollers 25, 27, 29, 31, 33, 35, 37, 39, 40, 41, 43, 45, 46, 47, 49, 51, 52, 53, 55, 57, 58, 59, 61, 63, 64, 65, 67, 69, 70, 71, 73, 75, 77, 79, 81, 83, 85, 87, 89, 91, 93 (hereinafter collectively referred to as a conveying roller group); a supply drum 101; a winding drum 103; a support table 105; a circulation filtration unit 107; six power supplies 109, 110, 111, 112, 113, 114; an end cleaning section 117; a recovery unit 119; and an end sensor 121.
The conveying roller group corresponds to a conveying unit. The power supplies 109, 110, 111, 112, 113, 114 correspond to connection units. In the present specification, the roller means a rotating object for conveying the electrode 1. The drum means an object having a cylindrical shape except the roller.
The electrolytic solution treatment tank 15 is a square tank having an open upper side. The bottom surface of the electrolytic solution treatment tank 15 has a substantially U-shaped cross-sectional shape. The electrolytic solution treatment tank 15 includes a separator 123. The partition 123 is supported by a support rod 125 penetrating the upper end of the partition 123. The support rod 125 is fixed to a wall or the like not shown. The partition 123 extends in the vertical direction and divides the inside of the electrolytic solution treatment tank 15 into two spaces.
A conveying roller 33 is mounted on the lower end of the partition 123. The partition 123 and the conveying roller 33 are supported by a support rod 127 penetrating the partition 123 and the conveying roller 33. Further, the vicinity of the lower end of the partition 123 is cut out so as not to contact the conveying roller 33. A space is provided between the conveying roller 33 and the bottom surface of the electrolytic solution treatment tank 15.
The structure of the doping trench 17 is explained with reference to fig. 4. The doping tank 17 includes an upstream tank 131 and a downstream tank 133. The upstream groove 131 is disposed on the supply drum 101 side (hereinafter referred to as upstream side), and the downstream groove 133 is disposed on the take-up drum 103 side (hereinafter referred to as downstream side).
The structure of the upstream tank 131 will be explained first. The upstream tank 131 is a square tank opened upward. The bottom surface of the upstream groove 131 has a substantially U-shaped cross-sectional shape. The upstream tank 131 includes a partition 135; and four counter electrode units 137, 139, 141, 143.
The partition 135 is supported by a support rod 145 penetrating the upper end of the partition 135. The support rod 145 is fixed to a wall or the like not shown. The partition 135 extends in the up-down direction and divides the inside of the upstream tank 131 into two spaces. A transfer roller 40 is installed at the lower end of the partition 135. The partition 135 and the transfer roller 40 are supported by a support rod 147 penetrating the partition 135 and the transfer roller 40. Further, the vicinity of the lower end of the partition 135 is cut out so as not to contact the transfer roller 40. A space exists between the conveying roller 40 and the bottom surface of the upstream slot 131.
The counter electrode unit 137 is disposed on the upstream side of the upstream groove 131. The counter electrode units 139, 141 are disposed so as to sandwich the separator 135 from both sides. The counter electrode unit 143 is disposed downstream of the upstream tank 131.
A space 149 exists between the counter electrode unit 137 and the counter electrode unit 139. A space 151 exists between the counter electrode unit 141 and the counter electrode unit 143. The counter electrode units 137, 139, 141, and 143 are connected to one electrode of the power supply 109. The counter electrode units 137, 139, 141, 143 have the same structure. Here, the structure of the counter electrode units 137 and 139 will be described with reference to fig. 5.
The counter electrode units 137 and 139 have a structure in which a conductive base 153, an alkali metal-containing plate 155, and a porous insulating member 157 are laminated. Examples of the material of the conductive base 153 include copper, stainless steel, and nickel. The form of the alkali metal-containing plate 155 is not particularly limited, and examples thereof include an alkali metal plate, an alkali metal alloy plate, and the like. The thickness of the alkali metal-containing plate 155 is, for example, 0.03 to 6 mm.
The porous insulating member 157 has a plate-like shape. The porous insulating member 157 is laminated on the alkali metal-containing plate 155. The shape of the porous insulating member 157 having a plate shape is a shape when the porous insulating member 157 is laminated on the alkali metal-containing plate 155. The porous insulating member 157 may be a member that itself retains a predetermined shape, or may be a member that can be easily deformed, such as a mesh.
The porous insulating member 157 is porous. Therefore, the doping solution described later can pass through the porous insulating member 157. Thereby, the alkali metal-containing plate 155 can be brought into contact with the doping solution.
Examples of the porous insulating member 157 include a mesh made of resin. Examples of the resin include polyethylene, polypropylene, nylon, polyether ether ketone, polytetrafluoroethylene, and the like. The mesh size of the screen can be appropriately set. The mesh size of the screen is, for example, 0.1 μm to 10mm, preferably 0.1 to 5 mm. The thickness of the screen can be set appropriately. The thickness of the mesh is, for example, 1 μm to 10mm, preferably 30 μm to 1 mm. The opening ratio of the screen can be appropriately set. The opening ratio of the screen is, for example, 5 to 98%, preferably 5 to 95%, and more preferably 50 to 95%.
The porous insulating member 157 may be entirely made of an insulating material, or may be partially provided with an insulating layer.
The downstream tank 133 has substantially the same structure as the upstream tank 131. However, the conveying roller 40 is not present inside the downstream groove 133 and the conveying roller 46 is present. The counter electrode units 137, 139, 141, and 143 of the downstream tank 133 are connected to one electrode of the power source 110.
The doping trench 19 has substantially the same structure as the doping trench 17. However, the interior of the doping tank 19 is not provided with transport rollers 40, 46 and transport rollers 52, 58. The counter electrode units 137, 139, 141, and 143 provided in the upstream tank 131 of the doping tank 19 are connected to one electrode of the power source 111. The counter electrode units 137, 139, 141, and 143 provided in the downstream groove 133 of the doping groove 19 are connected to one electrode of the power supply 112.
The doping trench 21 has substantially the same structure as the doping trench 17. However, the interior of the doping tank 21 is not provided with transport rollers 40, 46 and transport rollers 64, 70. The counter electrode units 137, 139, 141, and 143 provided in the upstream tank 131 of the doping tank 21 are connected to one electrode of the power source 113. The counter electrode units 137, 139, 141, and 143 provided in the downstream groove 133 of the doping groove 21 are connected to one electrode of the power supply 114.
The cleaning tank 23 has basically the same structure as the electrolytic solution treatment tank 15. However, the conveying roller 33 is not present inside the cleaning tank 23, and the conveying roller 75 is present.
The conveying rollers 37, 39, 43, 45, 49, 51, 55, 57, 61, 63, 67, 69 in the conveying roller group are formed of a conductive material. The other conveying rollers in the conveying roller group are formed of an elastomer except for bearing portions. The conveyance roller group conveys the electrode 1 along a predetermined path. The path of the conveying roller group conveying the electrode 1 is as follows: from the supply drum 101, the electrolyte solution passes through the electrolyte solution treatment tank 15, the doping tank 17, the doping tank 19, the doping tank 21, the cleaning tank 23, and the end cleaning section 117 in this order, and then reaches the winding drum 103.
The portion of the path that passes through the electrolytic solution treatment tank 15 is the following path: first, the sheet is moved downward by the conveying rollers 29 and 31, and then the moving direction is changed to an upward direction by the conveying roller 33.
Further, a portion of the above path passing through the doping groove 17 is a path: first, the conveying roller 37 changes the moving direction to the downward direction, and moves downward in the space 149 of the upstream slot 131. Then, the moving direction is changed to the upward direction by the conveying roller 40, and is moved upward in the space 151 of the upstream slot 131. Subsequently, the conveying rollers 41 and 43 change the moving direction to the downward direction, and move downward in the space 149 of the downstream groove 133. Then, the conveying roller 46 changes the moving direction to the upward direction, and moves upward in the space 151 of the downstream groove 133. Finally, the moving direction is changed to the horizontal direction by the conveying roller 47, and moved toward the doping tank 19.
Further, the portion of the above path passing through the doping groove 19 is the following path: first, the conveying roller 49 changes the moving direction to the downward direction, and moves downward in the space 149 of the upstream slot 131. Then, the conveying roller 52 changes the moving direction to the upward direction, and moves upward in the space 151 of the upstream slot 131. Subsequently, the conveying rollers 53 and 55 change the moving direction to the downward direction, and move downward in the space 149 of the downstream groove 133. Then, the conveying roller 58 changes the moving direction to the upward direction, and moves upward in the space 151 of the downstream groove 133. Finally, the moving direction is changed to the horizontal direction by the conveying roller 59, and moved toward the doping tank 21.
Further, a portion of the above path passing through the doping groove 21 is the following path: first, the conveying roller 61 changes the moving direction to the downward direction, and moves downward in the space 149 of the upstream slot 131. Then, the moving direction is changed to the upward direction by the conveying roller 64, and the sheet is moved upward in the space 151 of the upstream slot 131. Subsequently, the conveying rollers 65 and 67 change the moving direction to the downward direction, and move downward in the space 149 of the downstream groove 133. Then, the conveying roller 70 changes the moving direction to the upward direction, and moves upward in the space 151 of the downstream groove 133. Finally, the moving direction is changed to the horizontal direction by the conveying roller 71, and the cleaning tank 23 is moved.
Further, the portion of the above path that passes through the cleaning tank 23 is the following path: the moving direction is first changed to the downward direction by the conveying roller 73 and moved downward, and then changed to the upward direction by the conveying roller 75.
The supply roller 101 is wound with an electrode 1. That is, the supply roller 101 holds the electrode 1 in a wound state. The active material held in the electrode 1 of the supply roller 101 is not doped with an alkali metal.
The conveying roller group draws out and conveys the electrode 1 held by the feed roller 101. The winding drum 103 winds and holds the electrode 1 conveyed by the conveying roller group. Furthermore, the electrode 1 held by the winding drum 103 has been subjected to a preliminary doping treatment in the doping tanks 17, 19, 21. Therefore, the active material of the electrode 1 held by the winding drum 103 is doped with an alkali metal.
The support base 105 supports the electrolyte treatment tank 15, the doping tanks 17, 19, 21, and the cleaning tank 23 from below. The height of the support table 105 may vary. The doping tanks 17, 19, 21 are respectively provided with a circulation filter unit 107. The circulation filtration unit 107 includes a filter 161, a pump 163, and a pipe 165.
In the circulation filter unit 107 provided in the dope tank 17, the pipe 165 is a circulation pipe which is sent from the dope tank 17, then passes through the pump 163 and the filter 161 in order, and returns to the dope tank 17. The dope solution in the dope tank 17 is circulated in the pipe 165 and the filter 161 by the driving force of the pump 163 and returned to the dope tank 17 again. At this time, foreign substances and the like in the dope solution are filtered by the filter 161. Examples of the foreign matter include foreign matter precipitated from the doping solution, foreign matter generated from the electrode 1, and the like. The material of the filter 161 may be, for example, a resin such as polypropylene or polytetrafluoroethylene. The pore size of the filter 161 can be set as appropriate. The pore diameter of the filter 161 is, for example, 0.2 to 50 μm.
The circulation filter unit 107 provided in the doping tanks 19, 21 also has the same structure and achieves the same operation and effect. Note that, for convenience, the illustration of the doping solution is omitted in fig. 3 and 4.
One terminal of the power supply 109 is connected to the conveying rollers 37, 39. The other terminal of the power supply 109 is connected to the counter electrode units 137, 139, 141, and 143 provided in the upstream slot 131 of the doping slot 17. The electrode 1 is in contact with the transport rollers 37, 39. The electrode 1 and the counter electrode unit 137, 139, 141, 143 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 of the doping tank 17, the electrode 1 and the counter electrode units 137, 139, 141, 143 are electrically connected via the electrolytic solution.
One terminal of the power source 110 is connected to the conveying rollers 43, 45. The other terminal of the power source 110 is connected to the counter electrode units 137, 139, 141, and 143 provided in the downstream groove 133 of the doping groove 17. The electrode 1 is in contact with the conveying rollers 43, 45. The electrode 1 and the counter electrode unit 137, 139, 141, 143 are in a doping solution as an electrolyte. Therefore, in the downstream tank 133 of the doping tank 17, the electrode 1 and the counter electrode units 137, 139, 141, 143 are electrically connected via the electrolytic solution.
One terminal of the power source 111 is connected to the conveying rollers 49, 51. The other terminal of the power source 111 is connected to the counter electrode units 137, 139, 141, and 143 provided in the upstream slot 131 of the doping slot 19. The electrode 1 is in contact with the transport rollers 49, 51. The electrode 1 and the counter electrode unit 137, 139, 141, 143 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 of the doping tank 19, the electrode 1 and the counter electrode units 137, 139, 141, 143 are electrically connected via the electrolytic solution.
One terminal of the power supply 112 is connected to the conveying rollers 55, 57. The other terminal of the power source 112 is connected to the counter electrode units 137, 139, 141, and 143 provided in the downstream groove 133 of the doping groove 19. The electrode 1 is in contact with the conveying rollers 55, 57. The electrode 1 and the counter electrode unit 137, 139, 141, 143 are in a doping solution as an electrolyte. Therefore, in the downstream tank 133 of the doping tank 19, the electrode 1 and the counter electrode units 137, 139, 141, 143 are electrically connected via the electrolytic solution.
One terminal of the power source 113 is connected to the conveying rollers 61, 63. The other terminal of the power source 113 is connected to the counter electrode units 137, 139, 141, and 143 provided in the upstream slot 131 of the doping slot 21. The electrode 1 is in contact with the conveying rollers 61, 63. The electrode 1 and the counter electrode unit 137, 139, 141, 143 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 of the doping tank 21, the electrode 1 and the counter electrode units 137, 139, 141, 143 are electrically connected via the electrolytic solution.
One terminal of the power source 114 is connected to the conveying rollers 67, 69. The other terminal of the power supply 114 is connected to the counter electrode units 137, 139, 141, and 143 provided in the downstream groove 133 of the doping groove 21. The electrode 1 is in contact with the conveying rollers 67, 69. The electrode 1 and the counter electrode unit 137, 139, 141, 143 are in a doping solution as an electrolyte. Therefore, in the downstream tank 133 of the doping tank 21, the electrode 1 and the counter electrode units 137, 139, 141, 143 are electrically connected via the electrolytic solution.
The end cleaning section 117 cleans the end of the electrode 1 in the width direction W. Recovery units 119 are disposed in the electrolyte treatment tank 15, the doping tanks 17, 19, and 21, and the cleaning tank 23, respectively. The recovery unit 119 recovers the liquid carried out of the tank by the electrode 1 and returns the liquid to the tank. A specific structure of the recovery unit 119 will be described later. Among the recovery units 119, the recovery unit 119 disposed in the electrolyte treatment tank 15 corresponds to a recovery unit for the electrolyte treatment tank. Among the recovery units 119, the recovery unit 119 disposed in the cleaning tank 23 corresponds to a cleaning tank recovery unit.
The end sensor 121 detects the position of the end of the electrode 1 in the width direction W. An end position adjusting means, not shown, adjusts the positions of the supply roll 101 and the winding roll 103 in the width direction W based on the detection result of the end sensor 121. The end position adjusting unit adjusts the positions of the supply roller 101 and the take-up roller 103 in the width direction W so that the ends of the electrode 1 in the width direction W are at the positions cleaned by the end cleaning section 117.
3. Structure of recovery unit 119
The structure of the recovery unit 119 will be described with reference to fig. 6 and 7. The recovery unit 119 includes a fixed portion 171 and a rotating portion 173. The fixing portion 171 is fixed to a wall or the like not shown.
The fixing portion 171 includes a support plate 175, a removal roller 177, a transfer roller 179, a liquid discharge roller 181, a scraper 183, and a liquid droplet guide plate 185. The removal drum 177 and the removal drum 191 described later correspond to a recovery drum. Scraper 183 and scraper 197 described later correspond to a cleaning unit.
The support plate 175 is a plate-like member. The removal roller 177 is attached to the support plate 175 so as to be rotatable with respect to the support plate 175. The axial direction of the removing roller 177 is horizontally oriented and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group. The removing roller 177 is preferably formed of a material having elasticity except for a central shaft portion. The removing roller 177 is more preferably made of a porous material.
Examples of the material having elasticity include ethylene propylene diene monomer rubber, polyvinyl alcohol rubber, polyurethane rubber, polyolefin rubber, fluororubber, silicone rubber sponge, nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, isoprene rubber, butyl rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, epichlorohydrin rubber, and the like.
The transfer drum 179 is attached to the support plate 175 so as to be rotatable with respect to the support plate 175. The axial direction of the transfer cylinder 179 is parallel to the axial direction of the removal cylinder 177. The outer peripheral surface of the transfer cylinder 179 is in contact with the outer peripheral surface of the removal cylinder 177. The transfer roller 179 is formed of an elastic porous material except for a central shaft portion. Examples of the material forming the transfer drum 179 include porous materials such as ethylene propylene diene monomer rubber, polyvinyl alcohol rubber, polyurethane rubber, polyolefin rubber, fluororubber, silicone rubber sponge, nitrile rubber, hydrogenated acrylonitrile-butadiene rubber, isoprene rubber, butyl rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, epichlorohydrin rubber, and the like.
The drain cylinder 181 is rotatably attached to the support plate 175 with respect to the support plate 175. The axial direction of the drain roller 181 is parallel to the axial direction of the removing roller 177. The drain roller 181 is formed of a material harder than the material forming the transfer roller 179. The outer peripheral surface of the transfer cylinder 179 presses against the outer peripheral surface of the drain cylinder 181. This compresses the transfer cylinder 179 around the portion in contact with the drain cylinder 181, thereby reducing the volume.
The leading end 183A of the scraper 183 contacts the outer peripheral surface of the removal roller 177. The droplet guide 185 is a plate-shaped member. The droplet guide plate 185 is mounted to the support plate 175. The droplet guide 185 is positioned below the removal cylinder 177, the transfer cylinder 179, the drain cylinder 181, and the scraper 183. The droplet guide plate 185 is inclined so as to descend closer to the center of the recovery unit 119 in the width direction.
The rotating portion 173 is attached to the fixed portion 171 to be rotatable about a rotation axis 187 with respect to the fixed portion 171. The rotating unit 173 includes a support plate 189, a removing roller 191, a transfer roller 193, a drain roller 195, a scraper 197, and a droplet guide 199.
The support plate 189 is a plate-like member. The support plate 189 includes a rectangular main body portion 189A and a rod portion 189B. The rod portion 189B protrudes laterally from the vicinity of the upper end of the body portion 189A.
The removal drum 191 is attached to the body 189A so as to be rotatable with respect to the body 189A. The axial direction of the removing drum 191 is parallel to the axial direction of the removing drum 177. The removing roller 191 is preferably formed of a material having elasticity except for a central shaft portion. The removing roller 191 is more preferably formed of a porous material. The material forming the removing roller 191 is, for example, the same as the material forming the removing roller 177.
The transfer roller 193 is attached to the body 189A so as to be rotatable with respect to the body 189A. The axial direction of the transfer roller 193 is parallel to the axial direction of the removal roller 177. The outer circumferential surface of the transfer drum 193 contacts the outer circumferential surface of the removal drum 191. The transfer roller 193 is formed of an elastic porous material except for a central shaft portion. The material forming the transfer roller 193 is the same as the material forming the transfer roller 179, for example.
The drain roller 195 is attached to the body 189A so as to be rotatable with respect to the body 189A. The axial direction of the drain roller 195 is parallel to the axial direction of the removal roller 177. The drain roller 195 is formed of a material harder than the material forming the transfer roller 193. The outer peripheral surface of the transfer cylinder 193 is pressed against the outer peripheral surface of the drain cylinder 195. Thereby, the transfer roller 193 is compressed at the periphery of the portion in contact with the drain roller 195, and the volume is reduced.
A front end 197A of scraper 197 contacts the outer peripheral surface of removal drum 191. The droplet guide 199 is a plate-like member. The droplet guide 199 is mounted to the main body 189A. The droplet guide 199 is positioned below the removing cylinder 191, the transfer cylinder 193, the drain cylinder 195, and the scraper 197. The droplet guide 199 is inclined so as to descend closer to the center of the recovery unit 119 in the width direction.
A weight 201 is attached to the tip of the rod 189B. The rotating portion 173 is biased by the weight 201 so that the rotating portion 173 rotates in the X direction shown in fig. 6 and 7.
When the rotation portion 173 is rotated in the X direction, the recovery unit 119 is in a state shown in fig. 6 (hereinafter referred to as a 1 st state). In the 1 st state, the removing roller 177 and the removing roller 191 sandwich the electrode 1 from both sides. The removing roller 177 and the removing roller 191 are at a speed of 0.1g/cm2Above and 100kg/cm2The electrode 1 is pressurized by the following pressure. The pressure applied to the electrode 1 by the removing roller 177 and the removing roller 191 is preferably 1g/cm2Above 5kg/cm2Hereinafter, more preferably 5g/cm2Above and 500g/cm2The following. When the active material contained in the active material layer 5 is doped with an alkali metal, the recovery unit 119 is in the 1 st state.
When the rotation portion 173 is rotated in the Y direction shown in fig. 6 and 7, the recovery unit 119 is in a state shown in fig. 7 (hereinafter referred to as "state 2"). In the 2 nd state, the removing drum 191 is separated from the removing drum 177. In the 2 nd state, the removal rollers 177 and 191 do not pressurize the electrode 1. When the electrode 1 is conveyed, the recovery unit 119 is in the 2 nd state.
4. Components of the doping solution
When the doping system 11 is used, the electrolyte treatment tank 15 and the doping tanks 17, 19, and 21 contain a doping solution. The doping solution contains alkali metal ions and a solvent. The doping solution is an electrolyte.
Examples of the solvent include organic solvents. The organic solvent is preferably an aprotic organic solvent. Examples of the aprotic organic solvent include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1-fluoroethylene carbonate, γ -butyrolactone, acetonitrile, dimethoxyethane, tetrahydrofuran, dioxolane, methylene chloride, sulfolane, diethylene glycol dimethyl ether (diglyme), diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether (triglyme), triethylene glycol methyl butyl ether, tetraethylene glycol dimethyl ether (tetraglyme), and the like.
Further, as the organic solvent, an ionic liquid such as a quaternized imidazolium salt, a quaternized pyridinium salt, a quaternized pyrrolidinium salt, or a quaternized piperidinium salt can be used. The organic solvent may be composed of a single component, or may be a mixed solvent of two or more components. The organic solvent may be composed of a single component or a mixed solvent of two or more components.
The alkali metal ion contained in the doping solution is an ion constituting an alkali metal salt. The alkali metal salt is preferably a lithium salt or a sodium salt. Examples of the anion portion constituting the alkali metal salt include PF6 -、PF3(C2F5)3 -、PF3(CF3)3 -Phosphorus anions having a fluorine group; such as BF4 -、BF2(CF)2 -、BF3(CF3)-、B(CN)4 -Etc. a boron anion having a fluorine group or a cyano group; such as N (FSO)2)2 -、N(CF3SO2)2 -、N(C2F5SO2)2 -Sulfonyl imide anions having a fluorine group; such as CF3SO3 -And the like organic sulfonic acid anions having a fluorine group.
The concentration of the alkali metal salt in the dope solution is preferably 0.1 mol/L or more, and more preferably in the range of 0.5 to 1.5 mol/L. When the alkali metal salt is in this range, the preliminary doping of the alkali metal can be efficiently performed.
The dope solution may further contain additives such as vinylene carbonate, vinyl ethylene carbonate, 1-fluoroethylene carbonate, 1- (trifluoromethyl) ethylene carbonate, anhydrous succinic acid, anhydrous maleic acid, propane sultone, and diethyl sulfone.
The doping solution may further contain a flame retardant such as a phosphazene compound. From the viewpoint of effectively controlling the thermal runaway reaction when doping with an alkali metal, the amount of the flame retardant to be added is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and still more preferably 5 parts by mass or more, per 100 parts by mass of the dope solution. From the viewpoint of obtaining a high-quality doped electrode, the amount of the flame retardant to be added is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, per 100 parts by mass of the doped solution.
5. Method of using doping system 11
First, as preparation for doping the electrode 1, the following operation is performed. The electrode 1 is wound on the supply drum 101. Then, the electrode 1 is pulled out from the supply roll 101 and conveyed to the winding roll 103 along the above-described path. At this time, the recovery unit 119 is set to the 2 nd state. The electrolytic solution treatment tank 15, doping tanks 17, 19, 21, and cleaning tank 23 are raised and set at the fixed positions shown in fig. 3.
The electrolyte treatment tank 15 and the doping tanks 17, 19, and 21 contain doping solutions. The doping solution is the doping solution described in "4. composition of doping solution" above. The cleaning tank 23 contains a cleaning liquid. The cleaning solution is an organic solvent. The recovery unit 119 is set to the 1 st state.
Next, the electrode 1 is conveyed from the supply cylinder 101 to the winding cylinder 103 along the above-described path by the conveyance roller group. When the electrode 1 passes through the doping grooves 17, 19, 21, the active material contained in the active material layer 5 is doped with an alkali metal in advance.
The electrode 1 is conveyed by the conveying roller group and is simultaneously cleaned in the cleaning tank 23. Then, the electrode 1 is wound on the winding drum 103. The electrode 1 may be a positive electrode or a negative electrode. The doping system 11 dopes the positive electrode active material with an alkali metal when manufacturing the positive electrode, and the doping system 11 dopes the negative electrode active material with an alkali metal when manufacturing the negative electrode.
In the case where lithium is stored in the negative electrode active material of a lithium ion capacitor, the amount of alkali metal doped is preferably 70 to 95% of the theoretical capacity of the negative electrode active material, and in the case where lithium is stored in the negative electrode active material of a lithium ion secondary battery, the amount of alkali metal doped is preferably 10 to 30% of the theoretical capacity of the negative electrode active material.
6. Effects achieved by doping System 11
(1A) The doping system 11 includes a plurality of recovery units 119. The recovery units 119 are disposed in the electrolyte treatment tank 15, the doping tanks 17, 19, and 21, and the cleaning tank 23, respectively. The recovery unit 119 disposed in the doping tanks 17, 19, 21 suppresses the amount of the doping solution carried out of the doping tanks 17, 19, 21 by the electrode 1. The effect of the recovery unit 119 disposed in the doping tanks 17, 19, 21 will be described.
The electrode 1 having passed through the doping tanks 17, 19, 21 is moved upward and enters the recovery unit 119 as shown in fig. 6. The surface of the electrode 1 is attached with a doping solution. The removing rollers 177 and 191 sandwich the electrode 1 from both sides. The doping solution attached to the electrode 1 is absorbed by the removing rollers 177, 191.
The transfer roller 179 absorbs the dope solution contained in the removal roller 177. Therefore, the removing roller 177 can further absorb the doping solution attached to the electrode 1.
The transfer roller 193 absorbs the dope solution contained in the removal roller 191. Accordingly, the removing roller 191 can further absorb the doping solution attached to the electrode 1.
The drain roller 181 compresses the transfer roller 179. Therefore, the dopant solution contained in the transfer drum 179 is discharged from the transfer drum 179 and dropped. The dropped dope solution is returned to the dope tank 17, 19, 21 by being guided by the droplet guide plate 185. The transfer roller 179 can reabsorb the dopant solution contained in the removal roller 177 by discharging the dopant solution.
The drain roller 195 compresses the transfer roller 193. Therefore, the dope solution contained in the transfer roller 193 is discharged from the transfer roller 193 and dropped. The dropped dope solution is returned to the dope tanks 17, 19, 21 by being guided by the droplet guide 199. The transfer drum 193 discharges the dope solution, and thereby can further absorb and remove the dope solution contained in the drum 191.
As described above, the recovery unit 119 recovers the doping solution attached to the electrode 1 and returns the recovered doping solution to the doping tanks 17, 19, 21. Thus, the recovery unit 119 suppresses the amount of the dope solution carried out of the dope bath 17, 19, 21 by the electrode 1.
Similarly, the recovery unit 119 disposed in the electrolytic solution treatment tank 15 recovers the dopant solution adhering to the electrode 1, and returns the recovered dopant solution to the electrolytic solution treatment tank 15. Thereby, the recovery unit 119 suppresses the amount of the dope solution carried out of the electrode 1 from the electrolytic solution treatment tank 15.
Similarly, the recovery unit 119 disposed in the cleaning tank 23 recovers the cleaning liquid adhering to the electrode 1 and returns the recovered cleaning liquid to the cleaning tank 23. Thereby, the recovery unit 119 suppresses the amount of the cleaning liquid carried out of the cleaning tank 23 by the electrode 1.
(1B) The recovery unit 119 recovers the liquid using the removal rollers 177, 191. Therefore, the recovery unit 119 can recover the liquid more efficiently. The liquid is a doping solution or a cleaning solution.
(1C) The pressure applied to the electrode 1 by the removing rollers 177 and 191 was 0.1g/cm2Above and 100kg/cm2The following. By making the pressure applied to the electrode 1 0.1g/cm2As described above, the recovery unit 119 can recover the liquid more efficiently. By setting the pressure applied to the electrode 1 to 100kg/cm2The recovery unit 119 can suppress damage to the electrode 1.
(1D) The removing rollers 177 and 191 are formed of a material with elasticity. Therefore, the adhesion between the removing rollers 177 and 191 and the electrode 1 is high. Thereby, the recovery unit 119 can recover the liquid more efficiently.
(1E) The removing rollers 177 and 191 are preferably made of a porous material. When the removing rollers 177 and 191 are formed of a porous material, the removing rollers 177 and 191 can more easily absorb the liquid adhering to the electrode 1. Thereby, the recovery unit 119 can recover the liquid more efficiently.
(1F) The recovery unit 119 includes scrapers 183 and 197. The scraper 183 can clean the outer circumferential surface of the removal roller 177. Scraper 197 can clean the outer circumferential surface of removal drum 191.
By providing scrapers 183, 197 in recovery unit 119, it is possible to prevent dirt and the like on the outer circumferential surfaces of removal rollers 177, 191 from adhering to the surface of electrode 1.
< embodiment 2 >
1. Points different from embodiment 1
The basic configuration of embodiment 2 is the same as that of embodiment 1, and therefore, a different point will be described below. Note that the same reference numerals as those in embodiment 1 denote the same configurations as those in embodiment 1, and the above description is referred to.
In the above embodiment 1, the recovery unit 119 includes the transfer drums 179 and 193; and a drain roller 181, 195. Unlike embodiment 1, the recovery unit 119 does not include the transfer cylinders 179 and 193 and the drain cylinders 181 and 195 in embodiment 2.
2. Effects achieved by doping System 11
According to embodiment 2 described in detail above, in addition to effects (1B) to (1F) of embodiment 1 described above, the following effect can be achieved.
(2A) The doping system 11 includes a plurality of recovery units 119. The recovery units 119 are disposed in the electrolyte treatment tank 15, the doping tanks 17, 19, and 21, and the cleaning tank 23, respectively. The recovery unit 119 disposed in the doping tanks 17, 19, 21 suppresses the amount of the doping solution carried out of the doping tanks 17, 19, 21 by the electrode 1. The effect of the recovery unit 119 disposed in the doping tanks 17, 19, 21 will be described.
The electrode 1 having passed through the doping tanks 17, 19, 21 is moved upward and enters the recovery unit 119 as shown in fig. 8. The surface of the electrode 1 is attached with a doping solution. The removing rollers 177 and 191 sandwich the electrode 1 from both sides. The doping solution attached to the electrode 1 is absorbed by the removing rollers 177, 191.
If the amount of the dopant solution contained in the removing rollers 177 and 191 is large, the dopant solution drops from the removing rollers 177 and 191. The dropped dope solution is returned to the dope tanks 17, 19, 21 through the guidance of the droplet guide plates 185, 199.
As described above, the recovery unit 119 recovers the doping solution attached to the electrode 1 and returns the recovered doping solution to the doping tanks 17, 19, 21. Thus, the recovery unit 119 suppresses the amount of the dope solution carried out of the dope bath 17, 19, 21 by the electrode 1.
Similarly, the recovery unit 119 disposed in the electrolytic solution treatment tank 15 recovers the dopant solution adhering to the electrode 1, and returns the recovered dopant solution to the electrolytic solution treatment tank 15. Thereby, the recovery unit 119 suppresses the amount of the dope solution carried out of the electrode 1 from the electrolytic solution treatment tank 15.
Similarly, the recovery unit 119 disposed in the cleaning tank 23 recovers the cleaning liquid adhering to the electrode 1 and returns the recovered cleaning liquid to the cleaning tank 23. Thereby, the recovery unit 119 suppresses the amount of the cleaning liquid carried out of the cleaning tank 23 by the electrode 1.
< embodiment 3 >
1. Points different from embodiment 1
The basic configuration of embodiment 3 is the same as that of embodiment 1, and therefore, a different point will be described below. Note that the same reference numerals as those in embodiment 1 denote the same configurations as those in embodiment 1, and the above description is referred to.
As shown in fig. 9, doping system 11 according to embodiment 3 includes recovery unit 203 in addition to recovery unit 119. The recovery unit 203 is disposed above the recovery unit 119.
The recovery unit 203 has basically the same structure as the recovery unit 119. However, the recovery unit 203 does not include the droplet guide 185 and the droplet guide 199. The recovery unit 203 has the same function as the recovery unit 119.
The removing rollers 177 provided in the collecting unit 203 and the removing rollers 177 provided in the collecting unit 119 are arranged along the longitudinal direction of the electrode 1. Further, the removing drum 191 provided in the recovery unit 203 and the removing drum 191 provided in the recovery unit 119 are arranged along the longitudinal direction of the electrode 1.
2. Effects achieved by doping System 11
According to embodiment 3 described in detail above, in addition to the effects of embodiment 1 described above, the following effects can be achieved.
(3A) The doping system 11 includes a recovery unit 203 in addition to the recovery unit 119. Therefore, the doping system 11 can further suppress the amount of liquid carried out of the electrode 1 from the doping tanks 17, 19, 21, the electrolytic solution treatment tank 15, and the cleaning tank 23.
< embodiment 4 >
1. Points different from embodiment 1
The basic configuration of embodiment 4 is the same as that of embodiment 1, and therefore, a different point will be described below. Note that the same reference numerals as those in embodiment 1 denote the same configurations as those in embodiment 1, and the above description is referred to.
The doping system 11 according to embodiment 4 does not include the recovery unit 119 but includes the recovery unit 205 shown in fig. 10.
The recovery unit 205 is provided with a 1 st part 207 and a 2 nd part 209. The 1 st portion 207 and the 2 nd portion 209 are disposed so as to sandwich the electrode 1. The 1 st segment 207 is provided with a support plate 211 and two removal rollers 213, 215. The removing rollers 213, 215 correspond to the recovery rollers.
The support plate 211 is a plate-like member. The support plate 211 has an L-shape. The support plate 211 is attached to a wall or the like, not shown, so as to be rotatable about the rotation shaft 217. The axial direction of the rotary shaft 217 is horizontal and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group.
The removal rollers 213 and 215 are attached to the support plate 211 so as to be rotatable with respect to the support plate 211. The removal rollers 213, 215 are located below the rotating shaft 217. The removing drum 215 is located below the removing drum 213. In the 1 st state, the removing rollers 213 and 215 are in contact with the electrode 1. In the 1 st state, the removing rollers 213 and 215 are arranged along the longitudinal direction of the electrode 1. The axial directions of the removing rollers 213 and 215 are horizontally oriented and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group. The removing rollers 213 and 215 have the same structure as the removing roller 177 of embodiment 1.
The 2 nd part 209 is provided with a support plate 221, a support plate 223, removal rollers 225, 227, and a counterweight 233. The support plate 221 is a plate-like member. The support plate 221 has an L-shape. The support plate 221 includes a body portion 221A extending in the up-down direction, and a stem portion 221B extending in the lateral direction. The removing rollers 225, 227 correspond to recovery rollers.
The support plate 221 is attached to a wall or the like, not shown, so as to be rotatable about the rotation shaft 235. The rotation shaft 235 is located near the upper end of the body portion 221A. The axial direction of the rotary shaft 235 extends horizontally and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group.
A weight 233 is attached to the rod 221B. The support plate 211 is biased by the weight 233 so that the support plate 211 rotates in the a direction. The a direction is a direction in which the removing rollers 225 and 227 approach the electrode 1. The support plate 223 is a plate-like member extending in the vertical direction. The support plate 223 is attached to the support plate 221 so as to be rotatable about the rotation shaft 239 with respect to the support plate 221. The axial direction of the rotary shaft 239 extends horizontally and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group.
The removal rollers 225 and 227 are attached to the support plate 223 so as to be rotatable with respect to the support plate 223. The removal rollers 225, 227 are located below the rotary shaft 235. The removal drum 227 is located below the removal drum 225. In the 1 st state, the removing rollers 225 and 227 are in contact with the electrode 1. In the 1 st state, the removing rollers 225 and 227 are arranged along the longitudinal direction of the electrode 1. The removing rollers 225, 227 are oriented horizontally in the axial direction and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group. The removing drums 225 and 227 have the same configuration as the removing drum 191 in embodiment 1.
One end of the spring 229 is fixed to the support plate 221. The opposite end of the spring 229 is in contact with the portion of the support plate 223 that supports the removal roller 225. The spring 229 urges the removing roller 225 in the direction of the electrode 1. One end of the spring 231 is fixed to the support plate 221. The opposite end of the spring 231 is in contact with the portion of the support plate 223 that supports the removal roller 227. The spring 231 urges the removal roller 227 in the direction of the electrode 1.
A droplet guide 241 is disposed below the 1 st portion 207. The droplet guide 241 returns the liquid hanging down from the 1 st portion 207 to the doping tanks 17, 19, 21. A droplet guide plate 243 is disposed below the 2 nd portion 209. The droplet guide 243 returns the liquid hanging from the 2 nd portion 209 to the doping tanks 17, 19, 21.
2. Effects achieved by doping System 11
According to embodiment 4 described in detail above, in addition to the effects of embodiment 1 described above, the following effects can be achieved.
(4A) The doping system 11 includes removing rollers 213 and 215 arranged along the longitudinal direction of the electrode 1. The doping system 11 is provided with removing rollers 225 and 227 arranged along the longitudinal direction of the electrode 1. Therefore, the doping system 11 can further suppress the amount of liquid carried out of the electrode 1 from the doping tanks 17, 19, 21, the electrolytic solution treatment tank 15, and the cleaning tank 23.
(4B) The removal rollers 225, 227 are rotatable about a rotation axis 239 relative to the support plate 221. Therefore, in the doping system 11, it is easy to adjust the pressure at which the removal cylinders 225, 227 abut the electrode 1.
< embodiment 5 >
1. Points different from embodiment 1
Since the basic configuration of embodiment 5 is the same as that of embodiment 1, a different point will be described below. Note that the same reference numerals as those in embodiment 1 denote the same configurations as those in embodiment 1, and the above description is referred to.
The doping system 11 according to embodiment 5 does not include the recovery unit 119, but includes a recovery unit 245 shown in fig. 11.
The recovery unit 245 is provided with a 1 st section 247 and a 2 nd section 249. The 1 st portion 247 and the 2 nd portion 249 are arranged so as to sandwich the electrode 1. The 1 st section 247 includes a support plate 251 and four removing rollers 253, 255, 257, 259. The removing drums 253, 255, 257, 259 correspond to recovery drums.
The support plate 251 is a plate-like member. The support plate 251 is L-shaped. The support plate 251 is attached to a wall or the like, not shown, so as to be rotatable about the rotation shaft 261. The axial direction of the rotary shaft 261 is horizontal and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group.
The removing rollers 253, 255, 257, 259 are attached to the support plate 251 so as to be rotatable with respect to the support plate 251. The removing rollers 253, 255, 257, 259 are located below the rotating shaft 261. When in state 1, the removing rollers 253, 255, 257, 259 are in contact with the electrode 1. In the 1 st state, the removing rollers 253, 255, 257, 259 are arranged along the longitudinal direction of the electrode 1. The removing rollers 253, 255, 257, 259 have their axial directions oriented horizontally and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group. The removing rollers 253, 255, 257, 259 have the same structure as the removing roller 177 of embodiment 1.
The 2 nd part 249 is provided with a support plate 265, a support plate 267, a support plate 269, a support plate 271, removal rollers 273, 275, 277, 279, springs 281, 283, 285, 287, and a counterweight 289. The removing rollers 273, 275, 277, 279 correspond to the recovery rollers. The support plate 265 is a plate-like member. The support plate 265 has an L-shape. The support plate 265 includes a body portion 265A extending in the up-down direction, and a rod portion 265B extending in the lateral direction.
The support plate 265 is attached to a wall or the like, not shown, so as to be rotatable about the rotation shaft 291. The rotation shaft 291 is located near the upper end of the body 265A. The axial direction of the rotary shaft 291 extends horizontally and is parallel to the width direction W of the electrode 1 conveyed by the conveying roller group.
A weight 289 is attached to the rod 265B. The support plate 265 is urged by the weight 289 so that the support plate 265 rotates in the a direction. The a direction is a direction in which the removing rollers 273, 275, 277, 279 are brought close to the electrode 1.
The support plate 267 is a U-shaped plate member. The support plate 267 includes a central portion 267A, a 1 st arm portion 267B, and a 2 nd arm portion 267C. The central portion 267A extends in the vertical direction. The 1 st arm portion 267B extends in the direction of the electrode 1 from a position which is lowered 1/4 by the length of the central portion 267A from the upper end of the central portion 267A. The 2 nd arm portion 267C extends in the direction of the electrode 1 from a position 1/4 which is raised by the length of the central portion 267A from the lower end of the central portion 267A. The support plate 267 is attached to the support plate 265 so as to be rotatable about the rotation shaft 295 with respect to the support plate 265. The rotation shaft 295 is at the center in the up-down direction in the central portion 267A. The axis of the rotating shaft 295 extends horizontally and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group.
The support plate 269 is a plate-like member extending in the vertical direction. The support plate 269 is attached to the 1 st arm portion 267B so as to be rotatable about a rotation shaft 297 with respect to the 1 st arm portion 267B. The support plate 271 is a plate-like member extending in the vertical direction. The support plate 271 is attached to the 2 nd arm 267C so as to be rotatable about the rotation shaft 299 with respect to the 2 nd arm 267C. The axial directions of the rotary shafts 297 and 299 are horizontal and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group.
The removing rollers 273 and 275 are attached to the support plate 269 so as to be rotatable with respect to the support plate 269. In the 1 st state, the removing rollers 273 and 275 are in contact with the electrode 1. In the 1 st state, the removing rollers 273 and 275 are arranged along the longitudinal direction of the electrode 1. The removing rollers 273, 275 are oriented horizontally in the axial direction and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group. The removing drums 273 and 275 have the same configuration as the removing drum 191 in embodiment 1.
The removing rollers 277 and 279 are attached to the support plate 271 so as to be rotatable with respect to the support plate 271. When in state 1, the removing rollers 277 and 279 are in contact with the electrode 1. In the 1 st state, the removing rollers 277 and 279 are arranged along the longitudinal direction of the electrode 1. The axial direction of the removing rollers 277, 279 is horizontally oriented and parallel to the width direction W of the electrode 1 conveyed by the conveying roller group. The removing rollers 277 and 279 have the same structure as the removing roller 191 in embodiment 1.
One end of the spring 281 is fixed to the support plate 267. The opposite side end of the spring 281 contacts the portion of the support plate 269 that supports the removal roller 273. The spring 281 urges the removing drum 273 in the direction of the electrode 1.
One end of the spring 283 is fixed to the support plate 267. The opposite end of the spring 283 contacts the portion of the support plate 269 that supports the removal roller 275. The spring 283 urges the removing roller 275 in the direction of the electrode 1.
One end of the spring 285 is fixed to the support plate 267. The opposite end of the spring 285 contacts the portion of the backup plate 271 that supports the removal roller 277. The spring 285 biases the removing roller 277 in the direction of the electrode 1.
One end of the spring 287 is fixed to the support plate 267. The opposite side end of the spring 287 is in contact with the portion of the support plate 271 that supports the removal roller 279. The spring 287 biases the removing roller 279 in the direction of the electrode 1.
A droplet guide 241 is disposed below the 1 st section 247. The droplet guide 241 returns the liquid hanging from the 1 st section 247 to the doping tanks 17, 19, 21. A droplet guide plate 243 is disposed below the 2 nd portion 249. The droplet guide 243 returns the liquid dropped from the 2 nd portion 249 to the doping tanks 17, 19, 21.
2. Effects achieved by doping System 11
According to embodiment 5 described in detail above, in addition to the effects of embodiment 1 described above, the following effects can be achieved.
(5A) The doping system 11 includes removing rollers 253, 255, 257, 259 arranged along the longitudinal direction of the electrode 1. The doping system 11 is provided with removing rollers 273, 275, 277, 279 arranged along the longitudinal direction of the electrode 1. Therefore, the doping system 11 can further suppress the amount of liquid carried out of the electrode 1 from the doping tanks 17, 19, 21, the electrolytic solution treatment tank 15, and the cleaning tank 23.
(5B) The removal drums 273, 275 are rotatable about a rotation axis 297 with respect to the support plate 267. Furthermore, the removal rollers 277, 279 are rotatable relative to the support plate 267 about a rotation axis 299. The support plate 267 is rotatable about the rotation shaft 295 with respect to the support plate 265. Thus, in the doping system 11, it is easy to adjust the pressure at which the removal rolls 273, 275, 277, 279 abut the electrode 1.
< other embodiment >
The embodiments of the present disclosure have been described above, but the present disclosure is not limited to the above embodiments, and various modifications can be made.
(1) The recovery unit 119 may not include the removal rollers 177 and 191. For example, the recovery unit 119 may be provided with a member other than the roller, and press the member against the electrode 1. Further, the recovery unit 119 may remove the liquid from the electrode 1 by, for example, blowing air toward the electrode 1, vibrating the electrode 1, or the like, and return the liquid to the tank.
(2) The material forming the removing rollers 177,191 may be a solid material without elasticity. By solid material is meant a dense material or a material with little porosity. Examples of the solid material include polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, and polyether ether ketone resin.
(3) The method of applying force to the rotation portion 173 in the X direction may be another method. For example, the rotation portion 173 may be biased in the X direction by the elastic force of a spring.
(4) In the above embodiments, as the connection method of the power supply, the transport roller, and the electrode units of each pair, the transport roller and the electrode units of each pair are connected to different power supplies provided for each doping tank, but other methods are also possible. For example, a counter electrode unit facing one surface of the electrode 1 and a counter electrode unit facing the other surface may be connected to different power sources (hereinafter, referred to as a "mode a"). In the case of the mode a, the amount of the alkali metal doped to each surface of the electrode 1 is uniform.
In the embodiment a, the counter electrode units 137 and 143 provided in the upstream tank 131 of the doping tank 17 are connected to one electrode of the power supply 109. The counter electrode units 139 and 141 are connected to one electrode of the power supply 110. The counter electrode units 137 and 143 provided in the downstream groove 133 of the doping groove 17 are connected to the other electrode of the power supply 109. The counter electrode units 139 and 141 are connected to the other electrode of the power supply 110.
The counter electrode units 137 and 143 provided in the upstream tank 131 of the doping tank 19 are connected to one electrode of the power supply 111. The counter electrode units 139 and 141 are connected to one electrode of the power source 112. The counter electrode units 137 and 143 provided in the downstream groove 133 of the doping groove 17 are connected to the other electrode of the power supply 111. The counter electrode units 139 and 141 are connected to the other electrode of the power supply 112.
The counter electrode units 137 and 143 provided in the upstream tank 131 of the doping tank 21 are connected to one electrode of the power source 113. The counter electrode units 139 and 141 are connected to one electrode of the power source 114. The counter electrode units 137 and 143 provided in the downstream groove 133 of the doping groove 21 are connected to the other electrode of the power source 113. The counter electrode units 139 and 141 are connected to the other electrode of the power supply 114.
The conveying rollers 37, 41, 43, 47, 49, 53, 55, 59, 61, 65, 67, 71 in the conveying roller group are formed of a conductive material. The other conveying rollers in the conveying roller group are formed of an elastomer except for bearing portions.
One terminal of the power supply 109 is connected to the conveyance rollers 37, 41, 43, 47. The other terminal of the power supply 109 is connected to the counter electrode units 137 and 143 provided in the upstream tank 131 and the downstream tank 133 of the doping tank 17, respectively. The electrode 1 is in contact with the conveying rollers 37, 41, 43, 47. The electrode 1 and the counter electrode unit 137, 143 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 and the downstream tank 133 of the doping tank 17, the electrode 1 and the counter electrode units 137 and 143 are electrically connected via the electrolytic solution.
One terminal of the power source 110 is connected to the conveying rollers 37, 41, 43, 47. The other terminal of the power source 110 is connected to the counter electrode units 139 and 141 provided in the upstream tank 131 and the downstream tank 133 of the doping tank 17, respectively. The electrode 1 is in contact with the transport rollers 41, 47. The electrode 1 and the counter electrode unit 139, 141 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 and the downstream tank 133 of the doping tank 17, the electrode 1 and the counter electrode units 139 and 141 are electrically connected via the electrolytic solution.
In the embodiment a, as described above, the counter electrode units 137 and 143 facing the surface on one side of the electrode 1 are connected to one terminal of the power supply 109, and the counter electrode units 139 and 141 facing the surface on the other side of the electrode 1 are connected to one terminal of the power supply 110, whereby the amount of the alkali metal doped to the front side of the electrode 1 and the amount of the alkali metal doped to the back side of the electrode 1 can be controlled to be equal amounts.
One terminal of the power source 111 is connected to the conveyance rollers 49, 43, 55, 59. The other terminal of the power source 111 is connected to the counter electrode units 137 and 143 provided in the upstream tank 131 and the downstream tank 133 of the doping tank 19, respectively. The electrode 1 is in contact with the conveying rollers 49, 43, 55, 59. The electrode 1 and the counter electrode unit 137, 143 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 and the downstream tank 133 of the doping tank 19, the electrode 1 and the counter electrode units 137 and 143 are electrically connected via the electrolytic solution.
One terminal of the power supply 112 is connected to the conveying rollers 49, 43, 55, 59. The other terminal of the power supply 112 is connected to the counter electrode units 137 and 143 provided in the upstream tank 131 and the downstream tank 133 of the doping tank 19, respectively. The electrode 1 is in contact with the conveying rollers 49, 43, 55, 59. The electrode 1 and the counter electrode unit 137, 143 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 and the downstream tank 133 of the doping tank 19, the electrode 1 and the counter electrode units 137 and 143 are electrically connected via the electrolytic solution.
In the embodiment a, as described above, the counter electrode units 137 and 143 facing the surface on one side of the electrode 1 are connected to one terminal of the power source 111, and the counter electrode units 139 and 141 facing the surface on the other side of the electrode 1 are connected to the other terminal of the power source 112, whereby the amount of the alkali metal doped to the front side of the electrode 1 and the amount of the alkali metal doped to the back side of the electrode 1 can be controlled to be equal amounts.
One terminal of the power source 113 is connected to the conveying rollers 61, 65, 67, 71. The other terminal of the power source 113 is connected to the counter electrode units 137 and 143 provided in the upstream tank 131 and the downstream tank 133 of the doping tank 21, respectively. The electrode 1 is in contact with the conveying rollers 61, 65, 67, 71. The electrode 1 and the counter electrode unit 137, 143 are in a doping solution as an electrolyte. Therefore, in the upstream tank 131 and the downstream tank 133 of the doping tank 21, the electrode 1 and the counter electrode units 137 and 143 are electrically connected via the electrolytic solution.
One terminal of the power source 114 is connected to the conveying rollers 61, 65, 67, 71. The other terminal of the power supply 114 is connected to the counter electrode units 139 and 141 provided in the doping tank 21. The electrode 1 is in contact with the conveying rollers 61, 65, 67, 71. The electrode 1 and the counter electrode unit 139, 141 are in a doping solution as an electrolyte. Therefore, in the doping tank 21, the electrode 1 and the counter electrode units 139 and 141 are electrically connected via the electrolytic solution.
In the embodiment a, as described above, the counter electrode units 137 and 143 facing the surface on one side of the electrode 1 are connected to one terminal of the power source 113, and the counter electrode units 139 and 141 facing the surface on the other side of the electrode 1 are connected to the other terminal of the power source 114, whereby the amount of the alkali metal doped to the front side of the electrode 1 and the amount of the alkali metal doped to the back side of the electrode 1 can be controlled to be equal amounts.
(5) The functions of one constituent element in the above-described embodiments may be shared by a plurality of constituent elements, or the functions of a plurality of constituent elements may be exhibited by one constituent element. Further, a part of the configuration of each of the above embodiments may be omitted. Further, at least a part of the configuration of each of the embodiments may be added to the configuration of the other embodiments, or at least a part of the configuration of each of the embodiments may be replaced with the configuration of the other embodiments.
(6) The present disclosure can be realized in various forms other than the doping system described above, such as a system including the doping system as a constituent element, a program for causing a computer to function as a control device of the doping system, a non-transitory tangible recording medium such as a semiconductor memory in which the program is recorded, a doping method, an electrode manufacturing method, and an electrode manufacturing method.
< example >
(production of electrode 1 used in examples and comparative example 1)
A long strip-shaped current collector 3 is prepared. The current collector 3 is a negative electrode current collector. The dimensions of the current collector 3 are: 150mm in width, 100m in length and 8 μm in thickness. The surface roughness Ra of the current collector 3 was 0.1 μm. The current collector 3 is made of copper foil. Negative electrode active material layers 5 are formed on both surfaces of the current collector 3.
The coating amount of the negative electrode active material layer 5 formed on one side of the current collector 3 was 50g/m2. The negative electrode active material layer 5 is formed along the longitudinal direction of the current collector 3. The negative electrode active material layer 5 having a width of 130mm is formed from an end portion of the current collector 3 in the width direction W. The negative electrode active material layer non-formed portion at the other end portion of the current collector 3 in the width direction W was 20 mm. The negative electrode active material layer non-formation portion is a portion where the negative electrode active material layer 5 is not formed. Then, the electrode 1 is obtained by drying and performing pressing.
The anode active material layer 5 was formed by mixing, by mass, 88: 3: 5: 3: 1, a negative electrode active material, carboxymethyl cellulose, acetylene black, a binder, and a dispersant. The negative electrode active material is a mixture of a Si-based active material and a graphite-based active material. The negative electrode active material is prepared from the following components in a mass ratio of 2: 8 contains a Si-based active material and a graphite-based active material. Acetylene black corresponds to the conductive agent.
The doping system 11 shown in fig. 3 is prepared and the electrode 1 is transported. Further, the doping grooves 17, 19, 21 are each provided with a counter electrode unit 139, 141, 143. Then, the electrolytic solution is supplied into the doping tanks 17, 19, 21. The electrolyte is LiPF containing 1.0M6The solution of (1). The solvent of the electrolyte is 1: 1: 1 volume ratio of EC (ethylene carbonate) and EMC (carbon)Ethyl methyl carbonate), and DMC (dimethyl carbonate).
Then, the electrode 1 fed to the doping system 11 and the counter electrode units 139, 141, 143 were connected to a DC power supply with a current/voltage monitor, and the electrode 1 was fed at a speed of 0.1m/min while turning on the current of 5A. At this time, the center of the negative electrode active material layer 95 included in the electrode 1 in the width direction W coincides with the center of the lithium metal plate included in the counter electrode unit 51 in the width direction W. The energization time was set to a time at which the lithium doping ratio in the anode active material layer 5 reached 15% of the discharge capacity C2 of the anode, taking into consideration the irreversible capacity.
Further, the irreversible capacity was estimated in advance by measuring the discharge capacity of the electrode 1 after doping with lithium. Through this step, lithium is doped into the negative electrode active material in the negative electrode active material layer 95, and the electrode 1 is formed as a predoped negative electrode. The electrode 1 is a negative electrode for a lithium ion secondary battery.
The electrode 1 was wound after passing through the cleaning bath 7. DMC (dimethyl carbonate) at 25 ℃ is housed in cleaning tank 7. The electrode 1 subjected to the preliminary doping was manufactured in the above manner.
(example 1)
The electrode 1 manufactured as described above is conveyed again to the doping system 11. Further, the electrolytic solution is supplied into the doping tanks 17, 19, 21. The material of the removing roller 177 and the removing roller 191 is EPDM (ethylene propylene diene monomer). The pressure applied to the electrode 1 by the removing roller 177 and the removing roller 191 was 57.5g/cm2。
The electrode 1 was conveyed at a speed of 3m/min for 30 minutes. When the electrode 1 passes through the recovery unit 119, the electrode 1 is sandwiched between the removing rollers 177 and 191. The amount of decrease in the electrolytic solution in doping tanks 17, 19, 21 was 323 g. The amount of decrease in the amount of the electrolyte per 1m of the electrode 1 was 10.8 g/m.
(example 2)
Substantially the same operation as in example 1 was carried out. However, the pressure applied to the electrode 1 by the removing roller 177 and the removing roller 191 was set to 139.2g/cm2. Electricity in doping trenches 17, 19, 21The amount of reduction of the hydrolyzed solution was 209 g. The amount of decrease in the electrolyte per 1m of the electrode 1 was 7.0 g/m. The reason why the amount of decrease in the electrolytic solution in example 2 is smaller than that in example 1 is considered to be because: the contact between the removing roller 177, 191 and the electrode 1 is improved by increasing the pressure applied to the electrode 1 by the removing roller 177 and the removing roller 191, so that more electrolyte is returned to the doping tanks 17, 19, 21.
(example 3)
Substantially the same operation as in example 1 was carried out. However, the material of the removing roller 177 and the removing roller 191 is olefin sponge. The amount of decrease in the electrolytic solution in each of the doping tanks 17, 19, 21 was 230 g. The amount of decrease in the electrolyte per 1m of the electrode 1 was 7.7 g/m. The reason why the amount of decrease in the electrolytic solution in example 3 is smaller than that in example 1 is considered to be because: since the material of the removing rollers 177 and 191 is olefin sponge, even if the pressure applied to the electrode 1 by the removing rollers 177 and 191 is small, the contact between the removing rollers 177 and 191 and the electrode 1 can be improved, and more electrolyte can be returned to the doping tanks 17, 19, and 21.
In addition, the amount of reduction of the electrolytic solution in example 3 was not changed much from that in example 2. The reason for this is considered to be that: under the conditions of example 2 and example 3, the electrolyte adhering to the surface of the electrode 1 except the electrolyte impregnated in the electrode 1 was almost squeezed by the removing rollers 177 and 191 and returned to the doping tanks 17, 19, and 21.
(example 4)
Substantially the same operation as in example 3 was carried out. However, the pressure applied to the electrode 1 by the removing roller 177 and the removing roller 191 was set to 139.2g/cm2. The amount of decrease in the electrolytic solution in each of the doping tanks 17, 19, and 21 was 221 g. The amount of decrease in the electrolyte per 1m of the electrode 1 was 7.4 g/m.
From the above results, it is understood that when the material of the removing rollers 177 and 191 is olefin sponge, the amount of reduction of the electrolyte does not vary greatly even if the pressure applied to the electrode 1 is changed. The reason for this is considered to be that: the removing rollers 177 and 191 made of olefin sponge can sufficiently remove the electrolyte on the surface of the electrode 1 and return the electrolyte to the doping tanks 17, 19, and 21 even when the pressure applied to the electrode 1 is small.
Comparative example
Substantially the same operation as in example 1 was carried out. However, the removing roller 177 and the removing roller 191 are not used. The amount of decrease in the electrolytic solution in each of the doping tanks 17, 19, 21 was 840 g. The amount of decrease in the electrolyte per 1m of the electrode 1 was 28 g/m. From the above results, it was found that the amount of decrease in the electrolytic solution was increased to 2 times or more as compared with example 1 in the state where the conveyance speed was 3m/min and the removing rollers 177 and 191 were not used.

Claims (22)

1. A doping method of doping an active material in an electrode in a band shape with an alkali metal using a doping system, wherein the electrode has a layer containing the active material, the doping method being characterized in that,
the doping system is provided with:
a doping tank configured to accommodate a solution containing alkali metal ions;
a transport unit configured to transport the electrode along a path passing through the inside of the doping tank;
a counter electrode unit configured to be accommodated in the doping tank;
a connection unit configured to electrically connect the counter electrode unit and a conveyance roller provided in the conveyance unit; and
a recovery unit configured to recover the solution attached to the electrode that has passed through the doping tank, to the doping tank.
2. Doping method according to claim 1,
the recovery unit includes a recovery drum configured to recover the solution from the electrode.
3. Doping method according to claim 2,
the recovery drum is configured to pressurize the electrode.
4. Doping method according to claim 3,
the pressure applied by the recovery roller to the electrode is 0.1g/cm2Above and 100kg/cm2The following.
5. The doping method according to any one of claims 2 to 4,
at least a portion of the recovery drum is formed of a material with elasticity.
6. The doping method according to any one of claims 2 to 5,
at least a part of the recovery drum is formed of a porous material.
7. The doping method according to any one of claims 2 to 5,
at least a portion of the recovery drum is formed of a solid material.
8. The doping method according to any one of claims 2 to 7,
the doping system further includes a cleaning unit configured to clean a surface of the recovery drum.
9. The doping method according to any one of claims 2 to 8,
the doping system is provided with more than two recovery drums.
10. The doping method according to any one of claims 1 to 9,
the doping system further includes a cleaning tank configured to contain a cleaning solution,
the path is a path passing through the cleaning tank after passing through the doping tank,
the doping system further includes a cleaning tank recovery unit configured to recover the cleaning solution attached to the electrode having passed through the cleaning tank into the cleaning tank.
11. The doping method according to any one of claims 1 to 10,
the doping system further includes an electrolyte treatment tank configured to accommodate an electrolyte,
the path is a path through the electrolyte treatment bath before passing through the doping bath,
the doping system further includes an electrolyte treatment tank recovery unit configured to recover the electrolyte adhering to the electrode having passed through the electrolyte treatment tank into the electrolyte treatment tank.
12. A doping system for doping an active material in a strip-shaped electrode with an alkali metal, wherein the electrode has a layer containing the active material, the doping system comprising:
a doping tank configured to accommodate a solution containing alkali metal ions;
a transport unit configured to transport the electrode along a path passing through the inside of the doping tank;
a counter electrode unit configured to be accommodated in the doping tank;
a connection unit configured to electrically connect the counter electrode unit and a conveyance roller provided in the conveyance unit; and
a recovery unit configured to recover the solution attached to the electrode that has passed through the doping tank, to the doping tank.
13. The doping system of claim 12,
the recovery unit includes a recovery drum configured to recover the solution from the electrode.
14. The doping system of claim 13,
the recovery drum is configured to pressurize the electrode.
15. The doping system of claim 14,
the pressure applied by the recovery roller to the electrode is 0.1g/cm2Above and 100kg/cm2The following.
16. Doping system according to any of claims 13 to 15,
at least a portion of the recovery drum is formed of a material with elasticity.
17. Doping system according to any of claims 13 to 16,
at least a part of the recovery drum is formed of a porous material.
18. Doping system according to any of claims 13 to 16,
at least a portion of the recovery drum is formed of a solid material.
19. Doping system according to any of claims 13 to 18,
the doping system further includes a cleaning unit configured to clean a surface of the recovery drum.
20. Doping system according to any of claims 13 to 19,
the doping system is provided with more than two recovery drums.
21. Doping system according to any of claims 12 to 20,
the doping system further includes a cleaning tank configured to contain a cleaning solution,
the path is a path passing through the cleaning tank after passing through the doping tank,
the doping system further includes a cleaning tank recovery unit configured to recover the cleaning solution attached to the electrode having passed through the cleaning tank into the cleaning tank.
22. Doping system according to any of claims 12 to 21,
the doping system further includes an electrolyte treatment tank configured to accommodate an electrolyte,
the path is a path through the electrolyte treatment bath before passing through the doping bath,
the doping system further includes an electrolyte treatment tank recovery unit configured to recover the electrolyte adhering to the electrode having passed through the electrolyte treatment tank into the electrolyte treatment tank.
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